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Physical Chemistry: Electrochemistry I Dr. Rajeev Jain
Physical Chemistry: Electrochemistry I Dr. Rajeev Jain
Electrochemistry I
CONTENTS
1
Conductors, through which passage of an electric current through them results in actual transfer
of matter or brings about a chemical change in them, are called electrolytic conductors or electrolytes.
Electrolytic conductors are of two types: -
(a) In the first category are electrolytic conductors, which conduct electrolytically in the
pure state, such as acids, bases and salt in water. e.g. NaCl, NaNO3, K2SO4 etc.
(b) In second category are generally put electrolytic conductors which consists of solutions
of one or more substances. Electrochemistry is mainly concerned with this type of
electrolytic conductor.
Generally electrolytic solutions are prepared by dissolving a salt, acid or base in water or other
solvents. There is a special class of conductors, which conduct partly electronically and partly
electrolytically, are known as mixed conductors. For example, solution of the alkali and alkaline earth
metals in liquid ammonia are mixed conductors. Fused cuprous sulphide conducts electronically, but a
mixture with sodium or ferrous sulphide also shows electrolytic conduction.
2
1.2.2 Weak Electrolytes
Weak acids and weak bases, e.g., amines, phenols, most carboxylic acids and some inorganic
acids and bases, such as hydrocyanic acid and ammonia, and a few salts, e.g., mercuric chloride and
cyanide, are dissociated only to a small extent at reasonable concentration; this group of compounds in
general are called as weak electrolytes.
The molar conductance of the solutions of these electrolytes increases rapidly on dilution.
The reason of this is that more molecules ionize on dilution inspite of this they are never completely
ionized. For these electrolytes, the nature of the solvent is also important; a particular compound may
be strong electrolyte, being dissociated to large extent, in one solvent, but may behave as weak
electrolyte in other solvent due to low degree of dissociation.
¾ (c) & (d) are soluble hydroxides; (b) and (e) are first proton.
Fig. 1
3
Ohm’s law states that ‘The magnitude of current (I) passing through a conductor is directly
proportional to the potential difference (E) applied across it and inversely proportional to the resistance
(R) of the conductor’.
Q. The molar conductivity of a solution containing 2.54 g of CuSO4/L is 91.0 cm2/Ω.mole. What is the
resistance of a cm3 of this solution when placed between two electrodes 1.00 cm apart, each having an
area of 1.00 cm2.
κ N
¾ ∧= , where C = = mole/cm3
C 1000
⎛ 2.54 g of CuSO4 ⎞
⎜ ⎟ ⎛ 1mol ⎞ ⎛ 2mol ⎞
⎜ L ⎟ ⎜⎜ 159.5 g ⎟⎟ ⎜ mol ⎟ = 0.0318 M CuSO4
⎜ ⎟ ⎝ ⎠ ⎝ ⎠
⎝ ⎠
⎛ 91cm2 ⎞ ⎛ 0.0318mol ⎞
κ = ⎜⎜ ⎟⎟ ⎜ 3 ⎟
= 2.89 x 10-3 Scm-1
⎝ Ωmol ⎠ ⎝ 1000cm ⎠
We know that,
⎛ ⎞
1 ⎜
1 1 ⎟ ⎛ 1.00cm ⎞
R= . =⎜ ⎟ ⎜ 2 ⎟
= 346 Ω
κ A ⎜ 2.89 x 10− 3 Scm −1 ⎟ ⎝ 1.00cm ⎠
⎝ ⎠
E
i= (1)
R
Thus, metallic conductor and electrolytes obey Ohm’s law. Conductance is the reciprocal of resistance
and is expressed in Siemen (S).
1
Conductance = (2)
R
4
2.1 Specific Conductance or Conductivity
The resistance of the bar (Fig.1) to the passage of electricity through it is proportional to its
length ‘l’ (cm) and inversely proportional to the area of cross section ‘a’, therefore, the resistance ‘R’ is
given by the relationship.
1 1
R∝ or R = ρ ohms (3)
a a
Where, ‘ρ ‘ is a constant known as specific resistance or resistivity.
If, l = 1cm., a = 1 cm2
Then, ρ = R ohm cm
Specific conductance of any conducting material is defined as the reciprocal of its specific
resistance. It is given the symbol ‘κ’ and is stated in reciprocal ohm cm-1, nowadays called “Scm-1”.
Conductance ‘G’ is then defined as
a
G= κ S (4)
l
1
G= (5)
R
1
The conductance (G) is the reciprocal of resistance, i.e. G =
R
Where ν is the “dilution” of the solution in cc. per mole. If c is the concentration of the solution,
in mol /l, then ν is equal to 1000/c, then it becomes
κ
Λm = 1000 (7)
c
5
However if ‘c’ is expressed the equivalent conductance of any solution can thus be readily
derived from its specific conductance and concentration. Since the units of κ are S cm-1, those of Λm
comes out from eq. (6) or (7) to be Scm2 mol-1.
If one uses SI units then the units for ‘ρ’ is Ω m-1 for κ is Sm and for Λm is Sm2 mol-1. In earlier the
term equivalent conductance Λ was used. It is defined as the conductance of 1gram equivalent of
electrolyte in solution with a given concentration.
(A) (B)
Fig. 2: (A) Wheatstone bridge circuit for measurement of conductivity, (B) Conductivity cell with one
arm of a resistance bridge for measurement of conductivity of an electrolyte.
The arms AB and BC represented by resistance R1 and R2 are usually in the form of a single
calibrated slide wire resistor with a sliding contact connected to the null detector. The solution whose
conductance is to be determined is placed in conductivity cell. When the bridge is balanced, assuming
that the conductivity cell behaves as a pure resistance, then the voltage between ‘B’ and ‘D’ is equal to
zero.
⎛R ⎞
R ∧ = ⎜⎜ 1 ⎟⎟ x R3 (8)
⎝ R2 ⎠
6
By adjustment of the ratio R1/R2, a wide range of resistances can be measured. However,
whenever possible, this ratio should not deviate too far away from unity. The cell capacitance is
balanced out by providing a variable capacitor in parallel with resistance R3. It is so adjusted that the
detector gives a sharply defined balance point. The null detector is not an ordinary galvanometer as it is
not sensitive to alternating current at the frequency, which is employed to excite the bridge. The most
popular detector in use is the magic eye, or the cathode ray oscilloscope.
The problem in determining the resistance of the solution of an electrolyte by the above method
is that electrolysis of the solution also occurs simultaneously with the conduction of the current and due
to this: -
a) Polarisation sets in and causes the resistance to vary.
b) The concentration of the solution changes.
In order to avoid these complications an alternating source of power with frequency ~ 1000 Hz
is used.
7
with dilution. The variation of molar conductance at different dilutions of some common
electrolytes are shown Table 1:
Table 1: Molar Conductance of some common electrolytes at 250C in Scm2.
(ii) Effect of dilution on molar conductance is shown in the Figure.4, where the molar
conductance at different dilutions is plotted against concentration (M).
Molar Conductance
8
From Figure 3 it is clear that strong electrolytes such as KCl, can have limiting value at zero
concentration obtained by extrapolation (i.e. at infinite dilution) whereas for weak electrolyte such as
acetic acid, there is no indication that a limiting value can be obtained by the extrapolation of the graph
to zero concentration. It means we cannot experimentally determine molar conductivity of weak
electrolytes at infinite dilution.
(iii) The maximum value of the molar conductivity is termed as the molar conductivity at zero
concentration (or infinite dilution) and is termed ∧ ∞m .
0.000 0.012645
0.0005 0.012450
0.001 0.012374
0.01 0.011851
0.100 0.010674
Kohlrausch made a systematic study of ∧ ∞m for different electrolytes and concluded that each
ion contributes a characteristic value of its own to molar conductivity at infinite dilution irrespective of
the nature of the other ion present. Consider the values in Table.3 to appreciate the law:
9
Table.3: Values of Λo for different electrolytes
Electrolytes in set I and II have a common anion so that the difference can only be due to the
difference in contribution to Λ by K+ and Na+ ions. In the same way in sets III and IV the constant
difference may be attributed to the difference in contribution to ∧ ∞m made by the Cl- and NO3- ions.
These observations can be explained by Kohlrausch’s law of independent migration of ions which
states that:
At infinite dilution, where the electrolytes are fully dissociated and free from interionic effects,
each ion migrates independently of its co-ion. As such each ion contributes its definite share to the total
equivalent conductivity of the electrolyte, which depends only on the nature of the contributing ions
and not at all on the ion with which it is associated as a part of the electrolyte. In other words, the molar
conductivity at infinite dilution of an electrolyte is equal to the sum of the ionic conductances of the
ions composing it, provided the solvent and temperature are the same.
∧ ∞m = ν + ∧ ∞m + ν − ∧ ∞m (10)
Where, Λa and Λc are the ionic conductances of the anion and cation respectively at infinite
dilution and ν + and ν − is the number of cations and anions in which one molecule of the electrolyte. For
anion and cation this value is constant at a fixed temperature and in a given solution. It is expressed in
Scm2mol-1 or Sm2mole-1.
10
Q. The limiting molar conductivities of KCl, KNO3, and AgNO3 are 14.99 mSm2mol-1, 14.50 mSm2mol-1
and 13.34 mSm2mol-1 respectively at 25°C. Calculated the limiting molar conductivity of AgCl at this
temperature?
¾ The basis for the solution is Kohlrausch’s law of independent of ions. Switching
counterions does not affect the mobility of the remaining other ion at infinite dilution.
∧ ∞m = ν + λ + + ν − λ −
∧ ∞m (KCl) = λ ( K + ) + λ (Cl − ) = 14.99 mSm2mol-1
−
∧ ∞m (KNO3) = λ ( K + ) + λ ( NO3 ) = 14.50 mSm2mol-1
−
∧ ∞m (AgNO3) = λ ( Ag + ) + λ ( NO3 ) = 13.34 mSm2mol-1
∧ ∞m CH3COOH = x + y – z
11
5.1.2 Calculation of Degree of Dissociation of Weak Electrolytes
The degree of dissociation of weak electrolyte such as NH4OH, acetic acid can be determined by
measuring the molar conductivity Λ, of the solution of the electrolyte at any given dilution. For e.g. the
degree of dissociation (αc) of a weak electrolyte at the concentration C mole per liter may be given by
the following relation:
∧c
αc = (14)
∧∞
Where, Λc is the equivalent conductance of electrolyte at concentration ‘c’ and Λ∞ is the
equivalent conductance of the same electrolyte at infinite dilution. Hence, measurement of Λc permits
evaluation of ‘αc’ if Λ∞ is known.
∧ ∞m = κ .V (15)
Where, V is the volume in cm3 containing 1 mole of salt while ∧ ∞m , can be calculated using
Kohlraush’s law.
Substituting the values of κ and ∧ ∞m in eq. 15; below the value of V can be calculated:
V = ∧ ∞m / κ ≈ (ν + ∧ + + ν − ∧ − ) / κ (16)
But Vcm3 of saturated solution contains = 1 mole of salt
1000 cm3 of saturated solution contains= 1000 / V mole of salt
Hence, solubility of salt, S = 1000/V M
= 1000/V x M. Wt. = g/L
H2O H+ + OH-
The product of the concentrations of H+ and OH– ions expressed in mol/L is called ionic product of
water and is represented by Kw.
12
i.e. [H+] [OH-] = Kw
The measured specific conductivity of the purest form of water is 0.055 x 10-6 S cm-1. The
molar conductance is given by
Λm = Kv x 18 (17)
-6
Thus, = 0.055 x 10 x 18
= 0.990 x 10-6 Scm2mol-1
The molar conductance of water at infinite dilution can be obtained by
∧ ∞m (H2O) = Λ (H+) + Λ (OH-)
Therefore, Λ∞ (H2O) = 349.8 + 198.5 = 548.30 Scm2mol-1
and for water, α = Λm / Λ∞
= 0.055 x 10-3 x 18/ 548.3
CH+ = COH- = 0.055 x 10-3 x 18/ 548.3
(Concentration of water = 1000/18 = 55.55 M
CH+ = COH- = α x 55.55 x 10-9
= 1.806 x 55.55 = 1.003 x 10-7
Kw = (1.003 x 10-7)
= (1.006 x 10-14)
13
Q. Calculate the value of Kw for water in 0.100 M NaCl solution. The experimental value is 1.65 x 10-14.
¾ The thermodynamic value of the equilibrium constant for the dissociation of water
+ -
2H 2O H 3O + OH
a H O + + aOH −
Kw = 3
( a H 2O )
-14
= 1.01 x 10
Water is a liquid acting as a solvent, & its activity is its mole fraction, here 55.3/55.4 ≈ 1. Then
K w0 = [ H 3O + ] [OH − ]. f H O + . f OH −
3
K w0 = K w . f H O + f OH −
3
Where K w is the constant in terms of concentration activity coefficients from the extended Debye-
Huckel eqn., f H + = 0.825 and f OH − = 0.753.
3O
1.01 x 10 −14
Kw =
0.825 x 0.753
K w = 1.61 x 10-14
14
∧ ∞m = z ( u + + u − ) F (19)
6. Migration of Ions
As in a solution of an electrolyte the electricity is conducted by migration of ions and the ions
move in solution independently towards the oppositely charged electrodes. This fact can be illustrated
by following simple experiments:
(i) Lodge’s moving boundary evidence
A glass tube of the shape as shown in the Figure 4 is taken and its middle portion between two
arms is filled with a jelly of agar-agar. A trace of sodium hydroxide (or any alkali) and phenolphthalein
are added during the preparation of the jelly. It becomes red due to phenolphthalein in alkaline
medium. The jelly is allowed to set. After that dilute sulphuric acid is added to the left arm containing
the anode and sodium sulphate solution to the right arm in which the cathode is placed. On passing the
current, hydrogen ions migrate along the solution towards the cathode and their movement can be
monitored by observing the gradual fading of red colour in the jelly due to the neutralization of the
alkali by the hydrogen ions and the movement of the original boundary. Experiment clearly shows that
positively charged hydrogen ions (H+) are moving towards negatively charged cathode.
15
(A) (B)
In both the arms then a solution of potassium nitrate and agar-agar is filled. This on cooling also set as
jelly. Over this jelly, solution of potassium nitrate in distilled water is added and the electrodes are
immersed in it. With the application of potential difference across the electrode the blue colour of
copper ions rises in to the jelly towards the cathode. The reddish yellow dichromate ions move up in
the other arm of the tube towards the anode. In this experiment two types of ions can be clearly seen
moving with well-defined boundaries {Figure 5(B)}.
16
Fig. 6: Anodic and Cathodic compartments showing speeds of migration of ions
during electrolysis
In the Figure. 6 ‘A’ and ‘C’ are two porous diaphragms, which prevent convection currents but
allow the passage of ions. The cell is divided into an anodic and cathodic compartment. Suppose
initially 13 molecules were present. The number of molecules in each anode and cathode compartment
is equal i.e. 4 and 5 molecules are present between the two segment in ac {Fig.6(I)}.
Consider the following possibilities in reference to the above experiment.
(i) {Fig.6(II)} shows the movement of two anions alone, here only anions are capable of
movement.
(ii) Both anions and cations move at the same rate towards the opposite charged electrodes, the
condition as shown in {Fig.6 (III)}.
(iii) In another situation cations move at twice the rate of the anions (Fig.6 (IV)}.
In all the above conditions ions are always liberated in equivalent amounts; the effect of
difference in their rate only cause a change of concentration around electrodes. Further, from
the above experiment the following expression can be deduced.
17
Q. At 25°C the molar ionic conductivities of Li+, Na+, and K+ are 3.87 mSm2mol-1, 5.01 mSm2mol-1, and
7.35 mSm2mol-1 respectively. Calculate their mobilities.
λ
¾ We have, u =
zF
+ 3.87mSm 2 mol −1
(i) u ( Li ) =
96485Cmol −1
= 4.01 x 10-5 mSC-1m2
= 4.01 x 10-8 m2V-1s-1 (1CΩ = 1AsΩ = 1Vs)
+ 5.01mSm 2 mol −1
(ii) u ( Na ) =
96485Cmol −1
= 5.19 x 10-8 m2V-1s-1
7.35mSm 2 mol −1
(iii) u(K + ) =
96485Cmol −1
= 7.62 x 10-8 m2V-1s-1
18
From this interpretation of i , one obtains
i −1
α = (22)
ν −1
∧
This relation can also be used inspite of the relation α = , for calculating the degree of
∧ ∞m
dissociation of an electrolyte.
MA M+ + A- (23)
c (1-α) cα cα
cM + x c A− f M + x f A−
K= - (25)
c MA f MA
Here, ‘α’ is the degree of dissociation of electrolyte, i.e., the fraction of the electrolyte in the
form of free ions and c is its total concentration, (M). Both cM+ and cA- are equal to αC while cMA is
equal to c (1- α) then eq. (25) can be written as,
19
α 2c fM x f A
+ −
K= - (26)
(1 − α ) f MA
In sufficiently dilute solution the activity coefficient is approxiamately unity, then eq. (26) takes
the form:
α 2c
K= (27)
(1 − α )
This is the expression of the dilution law, first derived by W. Ostwald in 1988.
For weak electrolytes like acetic acid (CH3COOH) or ammonium hydroxide (NH4OH) the value
of degree of dissociation is very small, i.e., (1 – α) ≈1
eq. (27) can be written as;
K = α 2c (28)
K
α2= (29)
c
K
α = (30)
c
- +
CH3COOH CH 3COO + H
20
If c g moles of acetic acid are dissolved per liter of the solution and α is the degree of
dissociation, then the dissociation constant K is given by
α 2c
K= (32)
(1 − α )
If ‘ ∧ cm ’ is the equivalent conductance of the CH3COOH solution at the given dilution and ∧ ∞m at
∧ cm
infinite dilution, then α = (33)
∧ ∞m
Q. At 25°C, the molar conductance of propanoic acid at infinite dilution is 386.6 S cm2mol-1. If its
ionization constant is 1.4 x 10-5. Calculate molar conductance of 0.05 M propanoic acid solution at 25°C?
cx 2
¾ Ka = If x << 1 than Ka = cx2
(1 − x)
1.4 x 10 −5
Ka
Ka = = = 0.0167
c 0.05
∧ cm
x =
∧ ∞m
∧ cm = x x ∧ ∞m
= 0.0167 x 386.6
= 6.47 S cm2 mol-1
21
9.2 Applications of Ostwald’s Dilution Law
Applications of ostwald’s dilution law are many. Some of them are discussed below: -
[H ] [A ]
+ −
Ka = (36)
[HA]
22
[B ] [OH ]
+ −
α 2c
Kb = = (39)
[BOH ] (1 − α )
The value of ∧ cm of the solution is determined from its specific conductivity. ∧ ∞m of this solution
is calculated from ‘Kohlrausch law’ i.e.
∧ ∞m = ∧ ∞a + ∧ ∞c (43)
Where, ∧ ∞a and ∧ ∞a are ionic conductance of anion and cation of weak acids or bases.
By knowing the value of ∧ cm and ∧ ∞m values of α can be calculated. The dissociation constant can also
be calculated using equation (40).
23
Q. Molar conductivities at infinite dilution at 25°C of NH4Cl, NaOH and NaCl are 129.8, 217.4 & 108.9 S
cm2mol-1. For 0.01 M NaOH molar conductance is 9.33 S cm2mol-1. Calculate ionization constant of
NH4OH.
+ -
NH4OH NH4 + OH
¾
By Kohlrausch’s law
0.01 x (0.0392) 2
=
(1 − 0.0392)
= 1.6 x 10-5
24
electrolytes the value of molar conductance at infinite dilution is much less than unity due to following
effects:
25
Fig. 7. The dependence of molar conductivities on the square root of the ionic strength, and
comparison (shown by dotted lines) with the dependence predicted by the Debye-Huckel-Onsager
theory.
Figure 7 shows the dependence of molar conductivities on the square root of the ionic strength and
comparison with the dependence predicted by the Debye – Huckel – theory. The agreement is quite
good at very low molar concentrations (less than about 10-3 M, depending on the charge type).
Green – Kubo relationship can be applied on electric conduction, which expresses a transport properly
in terms of the fluctuations in microscopic properties of a system. The electrical conductivity is related
to the fluctuations in the sample that arises from variations in the velocities of the ions.
∞
1
κ=
KTV ∫ 〈 j (0) j (t )dt
0
(46)
N
j= ∑ z eν
i
i i (47)
where ν i is the velocity of the ion i at a given instant and the angular brackets denote an average
over the sample. If the ions are very mobile, there will be large fluctuations in the instantaneous
currents in the same, and the conductivity of the medium will be high. If the ions are locked into
position, as in an ionic solid, there will be no instantaneous currents, and the ionic conductivity will
be zero. The velocities of the ions are calculated explicitly in a molecular dynamics simulation, so
the correlation function, the quantity 〈 j (0 ) j (t ) , can be evaluated reasonably simply.
26
11.Transport Numbers
The transport number ( t ) is defined as the fraction of total current carried by the particular ionic
species in the solution. In a simple case of a single electrolyte yielding the ions designated by the
suffixes (+ )and (-), the corresponding transference numbers are given as follows:
q+
t+ = (48)
Q
Where q + is the quantity of electricity carried by the cation and Q is the total quantity of
electricity carried by all the ions through the solution. Similarly, the anion transport number t − is
defined as:
q−
t− = (49)
Q
Where q − is the quantity of electricity carried by the anion, equations (48) and (49) can be
expressed as
c+ u +
t+ = (50)
c+ u + + c− u −
c− u −
t− = (51)
c+ u + + c− u −
The quantities c + and c − which represent the concentrations of the ions, are equal and therefore
for this type of the electrolyte.
u+
t+ = (52)
u+ + u−
u−
t− = (53)
u+ + u−
and t + + t − = 1
27
u + and u − are the mobilities of the ions in the same solution and we know that the speed of an
ion in a solution at any concentration is proportional to the conductance of the ion at that concentration
and therefore the transference number may be represented in the form;
∧+ ∧
t+ = and t − = − (54)
∧m ∧m
Where the values of ∧ + and ∧ − (ion conductance) and Λm (molar conductance) of the solution,
are at that particular concentration at which the transference numbers are applicable.
This method of determining transport numbers was described as long ago as 1901.
Apparatus
To understand the principle involved consider the overall description of the method given
below. The apparatus consists of two separated compartments joined by a substantial middle
compartment and may be of any of the shape as shown in figure 8(A) and (B). Let us take silver nitrate
solution in a cell having silver electrodes. Before the experiment begins, the concentration of AgNO3 is
the same throughout the cell. The experiment involves passage of a direct electric current from a power
source through the cell.
28
(a) (b)
Fig.8: Hittorf’s cell
At the left-hand electrode, Ag dissolves and increases the AgNO3 concentration in its
compartment. In the right-hand compartment, Ag+ ions deposits so the AgNO3 concentration decreases
in the solution. Measurement of the changes in concentration in each compartment after a 2-3 h passage
of current yields the transport number of the anion (since t+ + t- = 1, it also gives that of the cation). The
current is passed for a fixed time. Thereafter, the anolyte (Figure 9) has an increased concentration c1
and the catholyte a decreased concentration c3. The middle compartment does not change its
concentration of silver nitrate, which will be designated c2.
Fig. 9: The Principle of Hittorf’s experiment (Adapted from J.O.M. Bockris and A.K.N. Reddy,
Modern Electrochemistry, volume I, 2nd edition, Plenam Press, N.Y. (1998)).
After t seconds (s) at current I, the number of moles of Ag introduced into the anolyte is
29
It
N= (55)
F
Where F is the faraday or electrical charge on one 1 mole of Ag+.
In the central compartment, in which the concentration is shown by experiment to remain
constant, current is given by the equation:
I = Ac2F (u+2 + u-2) (56)
Where ‘A’ is the cross sectional area of the central compartment and ‘u+2’ and ‘u-2’ are the ionic
mobilities, respectively, of Ag+ and NO3-. Therefore, from eq. (55) and (56),
N = Ac2 (u+2 + u-2)t (57)
In the left- hand compartment, Ag+ ions are produced and also moved out. Hence,
dN 1 1
= - Ac1u +1 (58)
dt F
According to principle of electroneutrality the concentration of both positive and negative ions in the
left -hand compartment should be the same. Therefore,
dN 1
= Ac 2 u − 2 (59)
dt
which represents the rate at which anions introduced by dissolution from the silver electrode move into
the left – hand compartment to join the cation. Integrating eq. (59) gives
N 1 − N 10 = Ac 2 u − 2 (60)
Where N 10 is the number of moles of AgNO3 in the compartment before the current I was switched on.
In the catholyte compartment, Ag+ ions are removed by deposition and transported from the
middle compartment,
dN 3 1
= Ac 2 u + 2 - (61)
dt F
NO3- moves out to allow elctroneutrality to be maintained. It must move out at the same rate as Ag+
disappears. Thus
dN 3
= - Ac3 u −3 (62)
dt
Integration of eq. (62) gives N 30 - N 3 = Ac3 u −3 t (63)
It has been assumed that the central compartment keeps a constant concentration while the
AgNO3 is increasing on the anolyte and decreasing in the catholyte.
30
0 0
Hence, N1 - N1 = N 3 - N 3 (64)
Now from eq. (57) and (60),
u −2 N − N 10 Gain in weight in anolyte
t− = = 1 = (65)
u +2 + u −2 N Loss of weight in anode
Again from eq. (57) and (63),
N 30 − N 3 Loss of weight of silver in catholyte
= (66)
N Gain in weight of cathode
Q. A solution containing 0.00739g of AgNO3 per gram of water was electrolyzed between silver
electrodes. During the experiment 0.0078g of silver was deposited in a silver coulometer placed in
series. At the end of experiment, the anodic solution contains 23.14g of water and 0.236g of AgNO3.
What are the transport number of Ag+ and NO3- ions?
Increase in concentration of Ag+ in the anodic compartment where no silver ions migrate =
0.0078
= 4.588 x 10-5
170
Increase in concentration of Ag+ in the anodic compartment when Ag+ ions migrate.
= Concentration of Ag after electrolysis – Concentration of Ag before electrolysis
= 5.992 x 10-5 – 4.347 x 10-5
= 1.645 x 10-5
Fall in concentration of Ag+ in anodic compartment
= 4.588 x 10-5 – 1.645 x 10-5
= 2.943 x 10-5
Fall in conc. around anode
+
Transport number of Ag ions =
Silver deposited on Ag electrode
2.943 x 10−5
= = 0.641
4.588 x 110− 5
Also transport number of NO3- ions can be calculated as
= 1 - t Ag +
= 1 – 0.641
= 0.359
31
11.1.2 Moving boundary method
The moving boundary method is based on measuring the rate of migration of one or both of the
ionic species of the electrolyte, away from the similarly charged electrodes and by this method we can
directly observe the migration of ions under the influence of an applied potential unlike the Hittrof’s
method in which concentration changes at the electrodes are observed. This method is very accurate
and has been used in recent years for precision measurements.
In the practical application of the moving boundary method one boundary only is observed, and
so the necessity of finding two indicator solutions is obviated; the method of calculation is as follows.
If one faraday of electricity passes through the system, ‘t+’ equiv. of the cation must pass at any given
point in one direction; if ‘c’ mole of the unit volume is the concentration of the solution in the vicinity
of the boundary formed by the ‘M’ ions, this boundary must pass through a volume t+ / c while one
faraday is passing. The volume ф taken out by the cations for the passage of Q coulombs is thus
Ф= Q t+/ F c (67)
Where F is one faraday, i.e., 96,500 coulombs. If the cross section of the tube in which the
boundary moves is α sq. cm., and the distance through which it moves during the passage of Q
coulombs is l cm., then Ф is equal to l α, and therefore from eq. (65)
t+ == l αF c / Q (68)
Since the number of coulombs passing can be determined, the transference number of the ion
may be calculated from the rate of movement of one boundary.
The apparatus used for the determination of the transport number by this method, consist a long vertical
tube of uniform bore fitted with two electrodes at the two ends as shown in figure 10.
32
Fig.10: Cell for the determination of transport number by moving boundary method
Let us consider the electrolyte AgNO3 the transport number of whose cation (Ag+) is to be
determined. A layer of a solution of AgNO3 is introduced above the solution of another suitable
electrolyte KNO3 having the common anion NO3-. The electrolyte KNO3 is selected so that the velocity
of K+ ions is less than those of Ag+ ions. Under the circumstances, there will be a clear-cut boundary
between the two electrolytes, even if the two solutions are colourless. On passing current between the
two electrodes, both Ag+ and K+ ions move upward towards the negative electrode while NO3- ions
move downward towards the positive electrode as shown in Figure 10. Since K+ ions have a lower
velocity than Ag+ ions, a sharp boundary is always maintained between the two solutions. Also the K+
ions are not far behind for if it so happens the solution below the boundary would get diluted and its
increasing resistance causes an increased potential drop thereby increasing the velocity of K+ ions.
Thus the boundary moves slowly in the upward direction. On passing n faraday of current, n x tAg+ will
be carried by Ag+ ions and a corresponding amount (n x tAg+) mole of it moves up. If c represents the
original concentration of Ag+ ions in mole ml-1 and the boundary moves through a distance l cm in the
tube of cross-section S cm2, the number of mole of Ag+ moving upward is given by S x l x C. Thus:
n x tAg+ = S x l x C (69)
33
S xl xC
or tAg+ = (70)
n
Knowing the experimental values of S, l, C and n, the value of tAg+ the transport number of Ag+ ions
can be calculated.
Q. In a moving boundary experiment 0.01 M HCl solution was treated on a lithium chloride solution.
The tube used had a diameter of 1 cm. when a current of 11.0 milliampere was passed for 20 min.,
the H+ ions – Li+ ions boundary moved through 13.9 cm. Calculate the transport number of H+, Cl-
ions in HCl solution used?
s x l x F x C
¾ We have, tH + =
Q
Also s = πr 2
22
= x 0.5 x 0.5
7
l = 13.9cm, F = 96500 coulomb, C = 0.01N
and tCl − = 1 - t H +
= 1 – 0.7984
= 0.2012
34
∧ ∞m (H3PO4) = ∧ ∞m (HCl) + ∧ ∞m (NaH2PO4) - ∧ ∞m (NaCl)
= 378.3 + 70.0 – 109.0
= 339.3
The measured value of ∧ m for 0.1M phosophoric acid is 96.5 Scm2mol-1 and the approximate
degree of dissociation is 96.5/339.3 i.e., 0.285 and the concentration of the ions is approximately
0.0285 M.
35
= 1.31 X 10-5 mole/L at 25o C.
12.4 Conductometric Titration
The determination of the end point of a titration by means of conductance measurements is
known as conductometric titration. In these titrations measurement of actual specific conductance of
the solution is not required, and any quantity proportional to it is sufficient. The titrant is added by a
burette and change of conductance as a function of added titrant is used to determine the equivalence
point. A conductance cell, in which solution of substance to be titrated is taken, consists of two
platinum electrodes of large surface area across which an alternating low-voltage potential is applied.
Generally, potential in the range 5-10Vat 1000 – 3000 Hz is employed. The conductance cell,
therefore, is incorporated into one arm of a Wheatstone bridge type of circuit and the conductance is
measured by adjustment of a calibrated resistor to balance the bridge.
Some typical examples of conductometric titration and interpretation of their curves are given
in following paragraphs. In all cases, the equivalence points are located at the intersection of lines of
differing slope. One of the requirements of these titrations is that the titrant should be at least ten times
as concentrated as the solution being titrated, in order to keep the volume change small.
12.4.1 Acid-Base Titration
(i) Strong Acid with a Strong Base
When a strong alkali, e.g., sodium hydroxide is added to a solution of a strong acid, e.g.,
hydrochloric acid, the following reaction occurs:
(H+ + Cl-) + (Na+ + OH-) = Na+ + Cl- + H2O
In this type of reaction, the conductance first falls, due to the replacement of the H+ ( ∧ ∞m = 350)
by the added cation Na+ ( ∧ ∞m = 40-80) and after the equivalence point has been reached, the
conductance rapidly rises with further addition of strong alkali due to large ∧ ∞m value of the hydroxyl
ion ( ∧ ∞m = 198). The two branches of the curve are straight lines provided the volume increase is
negligible and their intersection gives the endpoint. At the neutral point the conductance of the system
will have a minimum value, from which the equivalence point of the reaction can be determined.
A
Conductance
B
end point
mL of base (NaOH)
Fig. 11.(A)
36
In actual practice the lines may be slightly curved due to variation in temperature, heat of
neutralization, interionic effect and slight increase in the volume of the solution because of the addition
of titrant. Inspite of this, the inflection is sharp enough to get the end point.
(ii) Strong Acid with a Weak Base
The titration of a strong acid with a weak base may be illustrated by the neutralization of dilute
HCl by dilute NH4OH.
H+Cl- + NH4OH NH4+ + Cl- + H2O
The first branch of the graph (Figure.11B) represents the neutralization of the acid and its (i.e,
replacement of fast moving H+ ions by slow moving NH4+ ions). After the neutralization (end point) is
completed, the graph becomes almost horizontal, since the excess aqueous NH4OH is not appreciably
ionized in the presence of NH4Cl. As NH4OH is a weakly ionized electrolyte it has a very small
conductivity compared with that of the acid or its salt.
A
Conductance
end point
B
mL of base
Fig. 11 (B)
37
NaOH (strong)
Conductance
SAcid NH4OH (weak)
WAcid
mL of base
Fig. 12 (a)
Titrating reagent
Fig. 12 (b)
38
It is observed that such titrations curves are generally curved because the incompleteness of
reaction permits extra hydroxide ions (or hydrogen ions if a weak base is being titrated) to be present.
This causes an increase in conductivity. It is observed that with more incompleteness of the reaction,
the more curvature is observed in the graph.
(v) Mixture of a Strong Acid and a Weak Acid with a Strong Base
1) NaCl + H2O
(HCl + CH3COOH) + NaOH
2) CH3COONa + H2O
In such titration, the conductance decreases until the strong acid is neutralized and after that it
rises as the weak acid is converted into its salt. Finally the conductance rises more steeply as excess
alkali is introduced. The three branches of the curve will be straight lines except as: (i) increasing
dissociation of the weak acid results in a rounding off at the first end point. (ii) hydrolysis of the salt of
the weak acid causes a rounding off at the second end point. In case of rounding one can extrapolate to
get a sharp end point.
(II)
Conductance
(I)
Precipitant added
Fig. 13
In this reaction the highly ionized sodium acetate is replaced by highly ionized sodium chloride
and almost unionized acetic acid. Only a slight increase in conductance is observed up-to the end point
because chloride ion has slight by higher conductance than the acetate ion. After the end point is
passed, however, the free strong acid produces a marked increase, and its position can be determined
by the intersection of the two straight lines. (Figure 14).
39
Conductance
Titrating reagent
Fig. 14
Another example of such type of reactions is the salt of a weak base and a strong acid when
titrated by a strong base in an analogous manner.
NH4Cl + NaOH NH4OH + NaCl
12.4.3 Precipitation Reactions
Precipitation titration may also be carried out by conductometric methods. In reactions
of the type,
(K+ + Cl-) + (Ag+ + NO3-) AgCl + K+ + NO3-
and
(Mg2+ + SO42-) + 2(Na+ + OH-) Mg (OH)2 + 2Na+ + SO42-
Where a precipitate is formed, one salt is replaced by an equivalent amount of another, e.g.
potassium chloride by KNO3 and here the conductance remains almost constant before the end point.
After the equivalence point is passed, however, the excess KNO3 causes a sharp rise in the conductance
(Fig. 15, I); the end point of the reaction can thus be determined.
In another example, if both products of the reaction are sparingly soluble, the curve obtained takes up
the form as shown in (Fig.15, II), e.g.,
(Mg2+ + SO42-) + (Ba2+ + 2OH-) Mg (OH)2 + BaSO4
40
Conductance
Vol. of titrant added
Fig. 15
First, the conductance of the solution decreases but increases after the end point has passed.
Precipitation reactions, however, cannot be carried out accurately using conductance measurement due
to the following reasons.
(a) Slow separation of the precipitate,
(b) Removal of titrated solute by adsorption on precipitate
The best results are obtained by doing titration with dilute solutions in the presence of a relatively
large amount of alcohol, the presence of alcohol decreases the solubility of the precipitate and also
lesser adsorption.
(IV) Complexometric Titration Reactions
Conductometric titrations have also been employed in the determination of
stoichiometrey of complex compounds. For example, Job titrated roseo-cobaltic sulphate [CO(NH3)5
H2O]2 (SO4)3 with Ba(OH)2 and obtained two breaks in the titration curve (Figure 16). Also consider
the complexometric titrations of KCl with Hg (CO4)2, where two breaks are obtained in the curve as
shown in Figure 16.
Hg(ClO4)2 + 4KCl HgCl42- + 2K+ + 2KClO4
HgCl42- + 2K+ K2HgCl4
The first break is due to the formation of HgCl42- and the second is due to the formation of
K2HgCl4 at the end of the reaction.
41